Method for amnufacturing a semiconductor device

ABSTRACT

A method of manufacturing a semiconductor device includes forming a silicon nitride film having an opening portion on a semiconductor substrate, forming a silicon oxide film on the silicon nitride film and on a side face of the opening portion, performing an etching treatment to the silicon oxide film so that a sidewall is formed on the side face of the opening portion, forming a trench on the semiconductor substrate with use of the sidewall and the silicon nitride film as a mask, and forming an insulating layer in the trench. The step of forming the silicon oxide film includes oxidizing the silicon nitride film with a plasma oxidation method or a radical oxidation method.

TECHNICAL FIELD

This invention generally relates to a method for manufacturing asemiconductor device, and in particular, relates to a method formanufacturing a semiconductor device having an element separation regionusing a shallow trench isolation (STI) method.

BACKGROUND OF THE INVENTION

A Shallow Trench Isolation (STI) method is used as an clement separationmethod in a semiconductor device for the purpose of high integrationtherein. FIGS. 1A through 1D illustrate cross sectional views accountingfor element separation by an STI method in accordance with a firstconventional embodiment. As shown in FIG. 1A, a pad oxide film 12 and asilicon nitride film 14 are formed on a silicon semiconductor substrate10. An opening portion 22 is formed in a region of the pad oxide film 12and the silicon nitride film 14 where a trench is to be formed in thesubstrate 10.

As shown in FIG. 1B, the semiconductor substrate 10 is subjected to anetching process using the silicon nitride film 14 as a mask, and atrench 20 is formed in the semiconductor substrate 10. As shown in FIG.1C, the semiconductor substrate 10 inside the trench 20 is oxidized bythermal oxidation, and a trench oxide film 18 connecting to the padoxide film 12 is formed. As shown in FIG. 1D, a silicon oxide filmacting as an insulating film 30 is formed on the trench oxide film 18 inthe trench 20.

As shown in FIG. 2A, the silicon nitride film 14 is removed and, asshown in FIG. 2B, the pad oxide film 12 is also removed with an overalletching process. When the pad oxide film 12 is etched, an upper portionof the insulating film 30 is also etched. Thus, an insulating layer 34implanted in the trench 20 is formed from the trench oxide film 18 andthe insulating film 30, thereby enabling a STI separation.

xxxxxxxIn the first conventional embodiment, in FIG. 1C, there may begenerated a bird's beak on the trench 20 side at an interface betweenthe silicon nitride film 14 and the semiconductor substrate 10 duringthe formation of the trench oxide film 18. As a result, a face of thesemiconductor substrate 10 at the upper portion of the trench 20 may beinclined, as is case of a region 24. And as shown in FIG. 2B, an endportion of the insulating layer 34 and an end portion of the trench 20in which the bird's beak is generated are overlapped with each otherduring the formation of the insulating layer 34 of the STI. And, theetching may be performed in a horizontal direction, because the padoxide film 12 is removed with an isotropic etching. There may be formeda recess 26 composed of the semiconductor substrate 10 and theinsulating layer 34.

An art is disclosed below in order to restrain a formation of the recess26 in the first conventional embodiment. Japanese Patent ApplicationPublication No. 11-145275 (hereinafter referred to as Document 1)discloses an art where the semiconductor substrate 10 is immersed in HF(hydrofluoric acid)/glycerol after the process of FIG. 1C and thesilicon nitride film 14 is subjected to a side etching treatment asshown in FIG. 3. U.S. Pat. No. 5,521,422 (hereinafter referred to asDocument 2) discloses an art where a sidewall composed of a siliconoxide film is formed on a side face of the opening portion 22 of thesilicon nitride film 14 with a CVD method after the process of FIG. 1A.

In the art disclosed in Document 1, an etching speed of HF/glycerol withrespect to the silicon nitride film 14 is large, being 4.1 nm/minute. Ittakes very small time, 2.4 minutes, to etch a silicon nitride filmhaving a thickness of 10 nm. There may be variability in side etchingamount L1 of the silicon nitride film 14 shown in FIG. 3 in a wafer orbetween wafers treated at a time. Controllability is not good when thesilicon nitride film 14 is subjected to the side etching treatment,because the silicon nitride film 14 is side-etched and is backward. Thatis, there is a problem that controllability of a length L2 between eachof the silicon nitride films 14 is not good.

On the other hand, there is a problem with respect to the art disclosedin Document 2. FIG. 1A illustrates the side face of the opening portion22 of the silicon nitride film 14 being vertical to the surface of thesemiconductor substrate 10. In actual, it is difficult that the siliconnitride film 14 is etched vertically. The side face of the openingportion 22 of the silicon nitride film 14 is therefore formed to beoblique to the surface of the semiconductor substrate 10 as shown inFIG. 4A. A silicon oxide film 15 may be formed so as to have a smallthickness on the side face of the opening portion 22 as shown in FIG.4B, if the silicon oxide film 15 is formed on the oblique siliconnitride film 14 with a CVD method. A width L3 of a sidewall 16 istherefore reduced as shown in FIG. 4C. There may be variability in aninclination of the side face of the opening portion 22 of the siliconnitride film 14 from the surface of the semiconductor substrate 10, inthe wafer or between the wafers. There may be variability in thethickness of the silicon oxide film 15 on the side face of the openingportion 22. Further, there may be large variability in formation speedof the silicon oxide film 15 with respect to the CVD method. There maybe larger variability in the thickness of the silicon oxide film 15 onthe side face of the opening portion 22. The variability of the width L3is larger in the wafer or between the wafers, if the sidewall 16 isformed as shown in FIG. 4C. That is, the controllability of a distanceL2 between each of the silicon nitride films 14 is degraded.

As mentioned above, in the art disclosed in Document 1 and Document 2,the controllability of the distance L2 between each of the siliconnitride films 14 is not good. The controllability of the width of theinsulating layer 34 of the STI may get worse if the controllability ofthe distance L2 between each of the silicon nitride films 14 is notgood.

SUMMARY OF THE INVENTION

The present invention provides a method of manufacturing a semiconductordevice that restrains a formation of a recess of a trench and obtains acontrollability of a width of an insulating layer of the STI.

According to an aspect of the present invention, preferably, there isprovided a method of manufacturing a semiconductor device includingforming a silicon nitride film having an opening portion on asemiconductor substrate, forming a silicon oxide film on the siliconnitride film and on a side face of the opening portion, performing anetching treatment to the silicon oxide film so that a sidewall is formedon the side face of the opening portion, forming a trench on thesemiconductor substrate with use of the sidewall and the silicon nitridefilm as a mask, and forming an insulating layer in the trench. The stepof forming the silicon oxide film includes oxidizing the silicon nitridefilm with a plasma oxidation method or a radical oxidation method. Withthe method, it is possible to restrain a formation of the trench andimprove a controllability of a width of the insulating layer.

According to another aspect of the present invention, preferably, thereis provided a method of manufacturing a semiconductor device includingforming a silicon nitride film and a first silicon oxide film having anopening portion on a semiconductor substrate, forming a second siliconoxide film on an upper face of the first silicon oxide film and on aside face of the opening portion, performing an etching treatment to thefirst silicon oxide film so that the first silicon oxide film on thesilicon nitride film is left and forming a sidewall on the side face ofthe opening portion, forming a trench on the semiconductor substratewith use of the sidewall and the silicon nitride film as a mask, andforming an insulating layer in the trench. With the method, it ispossible to restrain a formation of the trench and improve acontrollability of a width or a shape of the trench.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A through FIG. 1D illustrate a cross sectional view accounting fora method of manufacturing a semiconductor device in accordance with afirst conventional embodiment;

FIG. 2A and FIG. 2B illustrate a cross sectional view accounting for themethod of manufacturing the semiconductor device in accordance with thefirst conventional embodiment;

FIG. 3 illustrates a problem of a method of manufacturing asemiconductor device disclosed in Document 1;

FIG. 4A through FIG. 4C illustrate a problem of a method ofmanufacturing a semiconductor device disclosed in Document 2;

FIG. 5A through FIG. 5E illustrate a method of manufacturing asemiconductor device in accordance with a first embodiment;

FIG. 6A through FIG. 6D illustrate the method of manufacturing thesemiconductor device in accordance with the first embodiment;

FIG. 7A illustrates a schematic SEM picture of a cross sectional view ofa semiconductor device manufactured with the method in accordance withthe first conventional embodiment;

FIG. 7B illustrates a schematic SEM picture of a cross sectional view ofa semiconductor device manufactured with the method in accordance withthe first embodiment;

FIG. 8A through FIG. 8D illustrate a method of manufacturing asemiconductor device in accordance with a second embodiment; and

FIG. 9A through FIG. 9C illustrate the method of manufacturing thesemiconductor device in accordance with the second embodiment.

DETAILED DESCRIPTION OF THE INVENTION

A description will now be given of best modes for carrying out thepresent invention.

First Embodiment

A description will be given of a method of manufacturing a semiconductordevice in accordance with a first embodiment, with reference to FIG. 5Athrough FIG. 6D. As shown in FIG. 5A, the pad oxide film 12 havingthickness t is formed on a silicon semiconductor substrate 10 withthermal oxidation method or the like. The thickness t is, for example,approximately 3 nm to 5 nm. The silicon nitride film 14 is formed on thepad oxide film 12 with a LP-CVD method or the like. Thickness of thesilicon nitride film 14 is, for example, approximately 100 nm.

As shown in FIG. 5B, a given region of the silicon nitride film 14 issubjected to an etching treatment with use of exposure technology andetching technology. And the opening portion 22 is formed so as to havewidth of, for example, 100 nm. With the process, there is formed thesilicon nitride film 14 having an opening portion on the semiconductorsubstrate 10.

As shown in FIG. 5C, the silicon oxide film 15 is formed on an upperface of the silicon nitride film 14 and on a side face of the openingportion 22 with a plasma oxidation method at, for example, 400 degreesC. As shown in FIG. 5D, the silicon oxide film 15 is subjected to anoverall etching treatment. And there is formed a sidewall 16 havingthickness W of, for example, 10 nm in a width direction thereof on theside face of the opening portion 22. The semiconductor substrate 10 isetched by for example 300 nm with use of the silicon nitride film 14 andthe sidewall 16 as a mask. And the trench 20 is formed. As shown in FIG.5E, a bottom face and a side face of the trench 20 are subjected to athermal oxidation treatment, and the trench oxide film 18 is formed.

As shown in FIG. 6A, a silicon oxide film acting as an insulating film31 is formed on the trench oxide film 18 in the trench 20 and on thesilicon nitride film 14 with a high density plasma CVD or the like sothat the trench 20 is implanted. As shown in FIG. 6B, the insulatingfilm 31 on the silicon nitride film 14 is polished with a CMP method.Thus, there is formed the insulating film 30 in the trench 20 andbetween the sidewalls 16.

As shown in FIG. 6C, the silicon nitride film 14 is removed withphosphoric acid or the like. As shown in FIG. 6D, the pad oxide film 12is removed with an overall etching using HF aqueous solution. In thiscase, an upper portion of the insulating film 30 is etched. Therefore,there is formed the insulating layer 34 implanted in the trench 20 fromthe trench oxide film 18 and the insulating film 30, and an STI isformed.

FIG. 7A illustrates a schematic view of a SEM picture around aninterface between the semiconductor substrate 10 and the insulatinglayer 34 having the STI structure manufactured with the manufacturingmethod in accordance with the first conventional embodiment. A recesshaving a depth of approximately 17.5 nm is formed on the surface aroundthe interface between the semiconductor substrate 10 and the insulatinglayer 34. On the other hand, FIG. 7B illustrates a schematic view of aSEM picture around an interface between the semiconductor substrate 10and the insulating layer 34 having the STI structure manufactured withthe manufacturing method in accordance with the first embodiment. Thereare few recesses on the surface around the interface between thesemiconductor substrate 10 and the insulating layer 34. This is becausean end portion of the trench 20 and an end portion of the insulatinglayer 34 are formed so as to be off each other because of the sidewall16 when the pad oxide film 12 is subjected to the etching treatment, asshown in FIG. 6D.

In FIG. 5C, the silicon oxide film 15 is formed with a plasma oxidationmethod. With the plasma oxidation method, it is possible to form thesilicon oxide film 15 evenly on the side face and the upper face of thesilicon nitride film 14. It is therefore possible to restrain avariability of width of the silicon oxide film 15 on the side face ofthe opening portion 22 as disclosed in Document 2, because ofinclination of the side face of the opening portion 22 of the siliconnitride film 14. And it is possible to improve controllability of thethickness of the silicon oxide film 15 with the plasma oxidation method,compared to a CVD method. It is therefore possible to improvecontrollability of a width L3 of the insulating layer 34 in FIG. 6D. Andit is possible to form the silicon oxide film 15 evenly on the side faceand the upper face of the silicon nitride film 14, with a radicaloxidation method. Accordingly, the silicon oxide film 15 shown in FIG.5C may be formed with the radical oxidation method instead of the plasmaoxidation method.

If the pad oxide film 12 shown in FIG. 6D is subjected to an etchingtreatment using HF aqueous solution as shown in the first embodiment,the etching is isotropic one. And so, the thickness W of the sidewall 16shown in FIG. 5A in the width direction thereof is set to be larger thanthe thickness t of the pad oxide film 12 shown in FIG. 5A. This overlapsthe end portion of the insulating layer 34 and the end portion of thetrench 20 with each other and prevents a recess like the recess 26 asshown in FIG. 2B of the first conventional embodiment from being formed.

Second Embodiment

Second embodiment is a case where a first silicon oxide film 28 isformed on the silicon nitride film 14. A description will be given of amethod of manufacturing a semiconductor device in accordance with thesecond embodiment, with reference to FIG. 8A through FIG. 9D. As shownin FIG. 8A, the first silicon oxide film 28 is formed on the siliconnitride film 14 with a CVD method, a plasma oxidation method or thelike, after the pad oxide film 12 and the silicon nitride film 14 areformed on the semiconductor substrate 10 as in the case of FIG. 5A ofthe first embodiment.

As shown in FIG. 8B, the opening portion 22 is formed in the firstsilicon oxide film 28 and the silicon nitride film 14. As shown in FIG.8C, the side face of the opening portion 22 of the silicon nitride film14 is oxidized with a plasma oxidation method and a second silicon oxidefilm 29 is formed. In this case, the thickness of the first siliconoxide film 28 on the silicon nitride film 14 and the thickness of thepad oxide film 12 on the bottom face of the opening portion 22 areslightly increased.

As shown in FIG. 8D, the first silicon oxide film 28 is subjected to anoverall anisotropic etching treatment so that the first silicon oxidefilm 28 is left on the silicon nitride film 14. And a sidewall 16 a isformed on the side face of the opening portion 22 of the silicon nitridefilm 14 from the second silicon oxide film 29. It is possible to formthe side face of the sidewall 16 a so as to be more vertical if thesidewall 16 a is formed in this way.

As shown in FIG. 9A, the trench 20 is formed in the semiconductorsubstrate 10 with use of the first silicon oxide film 28 as a mask. Asshown in FIG. 9B, the insulating film 30 is formed in the trench 20, asis in the case of FIG. 5D through FIG. 6B in the first embodiment. Inthis case, the first silicon oxide film 28 is removed during thepolishing. As shown in FIG. 9C, the silicon nitride film 14 and the padoxide film 12 are removed, as is in the case of FIG. 6C and FIG. 6D ofthe first embodiment. And the insulating layer 34 is formed in thetrench 20.

In accordance with the second embodiment, as shown in FIG. 8D, thesidewall 16 a is formed so that the first silicon oxide film 28 is lefton the silicon nitride film 14. It is therefore possible to form theside face of the sidewall 16 a more vertical to the semiconductorsubstrate 10, compared to the first embodiment. The controllability ofthe width or the shape of the trench 20 may be degraded when thesemiconductor substrate 10 shown in FIG. 9A is subjected to the etchingtreatment and the trench 20 is formed, if the side face of the sidewall16 is oblique. In the second embodiment, it is possible to improve thecontrollability of the width or the shape of the trench 20, because theside face of the sidewall 16 a is vertical.

Similarly to the second embodiment, it is possible to improve thecontrollability of the width or the shape of the trench 20 because ofthe formation of the second silicon oxide film 29 in FIG. 8C, if the CVDmethod or the like is used. However, it is possible to improve thecontrollability of the width of the insulating layer 34 with the plasmaoxidation method or the radical oxidation method, similarly to the firstembodiment.

While the above description constitutes the preferred embodiments of thepresent invention, it will be appreciated that the invention issusceptible of modification, variation and change without departing fromthe proper scope and fair meaning of the accompanying claims.

The present invention is based on Japanese Patent Application No.2006-355024 filed on Dec. 28, 2006, the entire disclosure of which ishereby incorporated by reference.

1-10. (canceled)
 11. A semiconductor device comprising: a siliconnitride film on a semiconductor substrate, the silicon nitride filmhaving an opening in a portion thereof; a silicon oxide film on thesilicon nitride film and on a side face of the opening wherein oxidationis on the silicon nitride film; a sidewall on the side face of theopening; a trench in the semiconductor; and an insulating layer in thetrench.
 12. The semiconductor device of claim 11, comprising a pad oxidefilm on the semiconductor substrate.
 13. The semiconductor device ofclaim 12, wherein a thickness of the sidewall is larger than a thicknessof the pad oxide film.
 14. The semiconductor device of claim 11, furthercomprising oxidation on a side face and a bottom face of the trench. 15.The semiconductor device of claim 11, wherein the insulating layer is anelement separation component.
 16. A semiconductor device comprising: asilicon nitride film and a first silicon oxide film on a semiconductorsubstrate, the silicon nitride film and the first silicon oxide filmhaving an opening formed in a portion thereof; a second silicon oxidefilm on an upper face of the first silicon oxide film and on a side faceof the opening; the second silicon oxide film so that the first siliconoxide film on the silicon nitride film is left and a sidewall on theside face of the opening; a trench in the semiconductor substrate; andan insulating layer in the trench.
 17. The device in accordance withclaim 16 further comprising a pad oxide film on the semiconductorsubstrate.
 18. The device in accordance with claim 17, wherein athickness of the sidewall is larger than a thickness of the pad oxidefilm.
 19. The device in accordance with claim 16 further comprisingoxide on a side face and a bottom face of the trench.